Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

VOLUME 54A

NUMBER 6

JUNE 2015

 

CONTENTS

 

 

709

 

Theoretical studies on the HM∙∙∙π (M=H, Li, Na, K) interactions involving the π-electron donors C2H2, C2H4 and C6H6

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jiang-Bo Xie*, Qiao-Ling Li, Wen-Jing Shi, Fu-de Ren & Hui Song

 

 

 

There is no clear distinction in the bonding nature between the
HM∙∙∙π and M∙∙∙π interactions (except for the H-Liπ and Liπ interactions), although the former is stronger than the latter.
A noticeable and unusual green RDG isosurface appears above the Li atom in the
Li∙∙∙π complexes, like a cap on the Li atom.

 

 

 

 

720

 

Does the more notable cooperativity correspond to
the higher stability? A comparative theoretical investigation on cooperativity effect upon addition of Na+ and F
into N-(Hydroxymethyl)acetamide dimer

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Wan-li Jia, Wen-jing Shi*, Fu-de Ren & Xiong Ding

 

 

 

The cooperative structure is more stable than the anti-cooperative structure for the F complex, while it is reverse for the Na+ system. The thermodynamic cooperativity is not in agreement with the cooperativity effect evaluated by interaction energy.

 

 

 

 

734

 

Functional modification of agarose: Synthesis of nanosize half-esters of succinic, phthalic and maleic acids

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Kondaveeti, N A Chudasama, J P Chaudhary,
R Meena & A K Siddhanta
*

 

 

 

A facile synthetic method for preparing new half-esters of agarose with succinic, phthalic and maleic acids, wherein the acid moieties are attached to the backbone of the agarose, is described. Dynamic light scattering measurements show that nano-sized polymeric vesicles (32-124 nm) are formed in aqueous solution. Ag-SA,
Ag-PA and Ag-MA
derivatives varying molar ratios of Ag/SA, Ag/PA and Ag/MA (1:11:5) show the highest degrees of substitution to be 0.89, 0.69 and 0.39 for Ag-SA (1:4), Ag-PA (1:3) and Ag-MA (1:2) respectively. Aqueous solutions of sodium salts of these esters exhibit enhanced electrical conductivity
(ca. 17.5 mS/cm at 40 C) as compared to those of the parent
half-esters (ca. 0.3 mS/cm at 40 C).

 

 

 

 

744

 

FeOx-VOx-WOx-MnOx-CeOx/TiO2 as a catalyst for selective catalytic reduction of NOx with NH3 and the role of iron

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Su Yu*, Dong Guojun*, Zhao Yuan,
Zhang Yufeng & Wang Yajie

 

 

 

FeOx-VOx-WOx-MnOx-CeOx/TiO2 catalyst prepared by ultrasound-substep-wet impregnation method for removing NOx from diesel engine exhausts demonstrates excellent low-temperature selective catalytic reduction activity over a broad temperature window of 150300 C. Results show that the excellent activity is due to the well-dispersed active components, the moderate ratio of V4+/V5+ and (Mn2++Mn3+)/Mn4+, the excellent redox property and the abundant acid sites. Iron plays the important role of inhibiting the agglomeration of metal oxide during the catalyst sintering and converting V and Mn to their higher oxidation states.

 

GA

 

 

Notes

 

752

 

Ru catalyzed formylation of diethylamine with CO2 and H2 under moderate pressure condition

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Aasif A Dabbawala, Sudheesh N & Hari C Bajaj*

 

 

 

Ru catalyzed formylation of diethylamine (bulky secondary amine) with CO2 and H2 is investigated using a series of phosphine ligands. The Ru catalyst with the ligand,
1,2-bis(diphenylphosphino)benzene exhibits the highest catalyst performance (TON up to 2475). The high conversion (99%) and high selectivity to the corresponding formamide (up to 90-98%) is achieved at 150 C and moderate pressure conditions.

 

 

 

 

757

 

Degradation of Acid Red 14 in contaminated water by Ag-SiO2 nanocomposite

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Shahla Masoudian*, Mohammad Hossein Rasoulifard & Parvaneh Pakravan

 

 

 

Silica aerogel doped with 12 wt% Ag, prepared by the alkoxide sol-gel method with tetraethyl orthosilicate as precursor, has been tested for degradation of Acid Red 14. Complete oxidation of the dye is achieved within 30 min under the optimum conditions.

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 709-719

 

 

Theoretical studies on HM∙∙∙π (M=H, Li, Na, K) interactions involving the
π-electron donors, C2H2, C2H4 and C6H6

Jiang-Bo Xie a,*, Qiao-Ling Li a, Wen-Jing Shib, Fu-de Renc & Hui Songc

aCollege of Materials Science and Engineering, North University of China, Taiyuan 030051, China

Email: xjb209@126.com

bThe Third Hospital of Shanxi Medical University, Taiyuan 030053, China

cCollege of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China

Received 27 October 2014; revised and accepted 18 May 2015

The intermolecular HM∙∙∙π (M=H, Li, Na, K) interactions involving the π-electron donors C2H2, C2H4 and C6H6 have been investigated using the DFT-B3LYP, MP2(full) and M06-2X methods with the 6-311++G(3df,2p) basis set. A comparison with the M∙∙∙π interaction in the corresponding M∙∙∙π complex has also been carried out. The results show that the HM∙∙∙π interaction energies follow the orders: HLi∙∙∙π > HNa∙∙∙π > HK∙∙∙π >> HH∙∙∙π and HM∙∙∙C6H6 > HM∙∙∙C2H4 ≈ HM∙∙∙C2H2. The HM∙∙∙π interaction is stronger than the M∙∙∙π interaction. The analyses of the natural bond orbital, atoms in molecules and electron density shifts reveal the nature of the HM∙∙∙π interactions and explain why C6H6 can form stronger complexes with HM. The reduced density gradient analysis indicates that except for the HLi∙∙∙π and Li∙∙∙π interactions, there is no clear distinction of bonding nature between the HM∙∙∙π and M∙∙∙π interactions. In the Li∙∙∙π complexes, an unusual green RDG isosurface appears above the Li atom, like a cap on the Li atom.

Keywords: Theoretical chemistry, Noncovalent interactions, Reduced density gradient, Intermolecular interactions, Electron density

 

Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 720-733

 

 

Does the more notable cooperativity correspond to the higher stability?
A comparative theoretical investigation on cooperativity effect upon
addition of Na+ and F
into N-(hydroxymethyl)acetamide dimer

Wan-li Jiaa, Wen-jing Shib, *, Fu-de Rena & Xiong Dinga5

aCollege of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China

bThe Third Hospital of Shanxi Medical University, Taiyuan 030053, China

Email: wenjingfd@126.com

Received 6 January 2015; revised and accepted 27 May 2015

The cooperativity effects between the O/NH∙∙∙O H-bonding and Na+∙∙∙O or O/NH∙∙∙F interactions in the
N-(hydroxymethyl)acetamide (HA) complexes with Na+ or F have been investigated using the B3LYP, MP2(full) and M06-2X methods with the 6-311++G** basis set. The thermodynamic cooperativities have also been studied.
The results show
the presence of cooperativity effects in HA∙∙∙HA∙∙∙Na+/F, while the anti-cooperativity effects are found in HA∙∙∙Na+/F∙∙∙HA. The cooperativity effects are seen preferably in the HA complexes with F, while the anti-cooperativity effects tend to be in the systems with Na+. The thermodynamic cooperativities in HA∙∙∙Na+/F∙∙∙HA are greater than those in HA∙∙∙HA∙∙∙Na+/F. Interestingly, the cooperative structure is more stable than the anti-cooperative structure for the complex with F while it is reverse for the Na+ system; the thermodynamic cooperativity is not in agreement with the cooperativity effect evaluated by interaction energy. The origin of stability and cooperativity effect has been examined by using the shifts of electron density and AIM (atoms in molecules) analyses.

Keywords: Theoretical chemistry, Cooperativity effect, Stability, Hydrogen bond, Thermodynamic cooperativity, Electron density

 

Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 734-743

 

 

Functional modification of agarose: Synthesis of nanosize half-esters of succinic, phthalic and maleic acids

S Kondaveetia, N A Chudasamaa, J P Chaudharya, b, R Meenaa, b & A K Siddhantaa, b, *

aMarine Biotechnology and Ecology Discipline, CSIR-Central Salt & Marine Chemicals Research Institute,
G B Marg, Bhavnagar 364 002, Gujarat, India

bAcademy of Scientific & Innovative Research, Anusandhan Bhavan, 2 Rafi Marg,
New Delhi 110 001, India

Email: aks@csmcri.org

Received 1 April 2015; accepted 29 May 2015

A facile synthetic method for preparing new half-esters of agarose (Ag) with succinic (SA), phthalic (PA) and maleic (MA) acids has been described. The half-esters (Ag-SA, Ag-PA and Ag-MA) wherein the acid moieties are attached to the backbone of the agarose are characterized. Dynamic light scattering measurements show that nano-sized polymeric vesicles (32-124 nm) are formed in aqueous solution. A series of Ag-SA, Ag-PA and Ag-MA derivatives have been prepared with degrees of substitution ranging from 0.36 to 0.89 using varying molar ratios of Ag/SA, Ag/PA and Ag/MA (1:11:5). The highest degrees of substitution are found to be 0.89, 0.69 and 0.39 for Ag-SA (1:4), Ag-PA (1:3) and Ag-MA (1:2) respectively. The aqueous solution of sodium salts of these esters exhibit enhanced electrical conductivity (ca. 17.5 mS/cm at 40 C) as compared to those of the parent half-esters (ca. 0.3 mS/cm at 40 C). These new agarose based nanosized materials may have potential applications in electrochemical devices, sensors and as drug carriers.

Keywords: Agarose, Polysaccharides, Functional modification, Succinoylation, Phthaloylation, Maleoylation

 

Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 744-751

 

 

FeOx-VOx-WOx-MnOx-CeOx/TiO2 as a catalyst for selective catalytic reduction of NOx with NH3 and the role of iron

Su Yua, *, Dong Guojun*,b, Zhao Yuanb, Zhang Yufengb & Wang Yajieb

aSchool of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, PR China

Email: suyu-0451@163.com

bCollege of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin, 150001, PR China

Email: dgj1129@163.com

Received 3 February 2015; revised and accepted 29 May 2015

The preparation of FeOx-VOx-WOx-MnOx-CeOx/TiO2 catalyst by the ultrasound-substep-wet impregnation method for removing NOx from diesel engine exhausts has been demonstrated along with the excellent low-temperature selective catalytic reduction activity over a broad temperature window of 150300 C. The specific surface area, catalyst structure, composition and SCR reactivity tests of NO with NH3 at low temperatures have been investigated by nitrogen adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, H2 temperature programmed reduction, NH3 temperature programmed desorption and in situ DRIFTS measurements. The results show that the excellent activity is due to the well-dispersed active components, the moderate ratio of V4+/V5+ and (Mn2++Mn3+)/Mn4+, the excellent redox property and the abundant acid sites. Iron plays the important role of inhibiting the agglomeration of metal oxide during the catalyst sintering and converting
V and Mn to their higher oxidation states
.

Keywords: Catalysts, Oxides, Nitrogen oxides, Reduction, Iron, Vanadium, Tungsten, Manganese, Cerium, Titanium

 

Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 752-756

 

 

Ru catalyzed formylation of diethylamine with CO2 and H2
under moderate pressure condition

Aasif A Dabbawala, Sudheesh N & Hari C Bajaj*

Division of Inorganic Materials and Catalysis, Central Salt and Marine Chemicals Research Institute
(CSIR-CSMCRI), Council of Scientific and Industrial Research, G B Marg, Bhavnagar 364 002, Gujarat, India

Email: hcbajaj@csmcri.org

Received 23 April 2015; accepted 26 May 2015

Ru catalyzed formylation of diethylamine (bulky secondary amine) with CO2 and H2 has been investigated using a series of phosphine ligands. Significant influence on the catalyst activity and selectivity is observed with bidentate phosphine ligands. The Ru catalyst with the ligand, 1,2-bis(diphenylphosphino)benzene exhibits the highest catalyst performance (TON up to 2475). The high conversion (99%) and high selectivity to the corresponding formamide (up to 90-98%) is achieved at 150 C and moderate pressure conditions. The effects of temperature, concentration of diethylamine and partial pressure of CO2 and H2 on the formylation of diethyl amine catalyzed have been examined in order to improve the catalytic activity and selectivity.

Keywords: Catalysis, Formylation, Diethyl amine, Carbon dioxide, Ruthenium, Bidentate phosphines

 

Indian Journal of Chemistry

Vol. 54A, June 2015, pp. 757-761

 

 

Degradation of Acid Red 14 in contaminated water by Ag-SiO2 nanocomposite

Shahla Masoudiana,*, Mohammad Hossein Rasoulifardb & Parvaneh Pakravana

aDepartment of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran

bWater and Wastewater Treatment Research Laboratory, Department of Chemistry,

Faculty of Science, University of Zanjan, Zanjan, Iran

Email: sh_m_chem@yahoo.com

Received 3 February 2014; revised and accepted 2 May 2015

An aerogel of silica gel doped with 12 wt% Ag has been prepared by an alkoxide sol-gel method with tetraethyl orthosilicate as precursor material, and calcined at 500 C to produce nanoparticle solids. This nanomaterial has
been characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and Brunauer-Emmett-Teller data. The nanosized silver-silica gel mixed oxide has been tested for the oxidation of the azo dye, Acid Red 14, using peroxidisulfate as oxidant. The 12 wt% Ag loaded SiO2 shows very good efficiency in degradation of the dye. The effects of various parameters including solution pH, catalyst, oxidant and initial dye concentrations on degradation have been investigated and the optimum conditions determined. The catalyst is resistant to leaching and can be recycled several times without appreciable loss of activity.

Keywords: Nanocomposites, Composites, Degradation, Dye degradation, Sol-gel method, Peroxidisulfate